Fungicidal compositions containing piperidine compounds

ABSTRACT

This invention provides fungicidal compositions comprising as an active ingredient a compound having the general formula (I): ##STR1## or a stereoisomer thereof, wherein one of X and Y represents hydrogen and the other represents the group ##STR2## in which R is hydrogen, methyl or ethyl; Z represents hydrogen or an alkyl group containing from one to four carbon atoms; R 1  and R 2 , which may be the same or different, represent hydrogen or an alkyl group containing one to four carbon atoms, or R 1  and R 2  together with the adjacent nitrogen atom represent an optionally-substituted heterocyclic ring; and n is 0 or 1.

This invention relates to fungicidal compositions containing organicamine compounds, and to methods of using them to combat fungi,especially fungal infections in plants; the invention also relates tocertain of those compounds which are novel per se.

This invention provides fungicidal compositions comprising as an activeingredient a compound having the general formula (I): ##STR3## or astereoisomer thereof, wherein one of X and Y represents hydrogen and theother represents the group ##STR4## in which R is hydrogen, methyl orethyl; Z represents hydrogen or an alkyl group containing from one tofour carbon atoms; R¹ and R², which may be the same or different,represent hydrogen or an alkyl group containing one to four carbonatoms, or R¹ and R² together with the adjacent nitrogen atom representan optionally-substituted heterocyclic ring; and n is 0 or 1.

Preferably R¹ and R², together with the adjacent N-atom, represent theresidue of a tertiary amine, and it is further preferred that theyrepresent a heterocyclic ring; this may be, for example, a piperidine,pyrrolidine, piperazine or morpholine ring which may be optionallysubstituted by one or more groups alkyl (itself optionally substituted)containing one to four carbon atoms, aryl (itself optionallysubstituted), hydroxy, alkoxy, or aryloxy (itself optionallysubstituted) or aralkyl (itself optionally substituted).

Particularly preferred heterocyclic rings which are thus represented arethe piperidine and 2,6-dimethylmorpholine ring systems.

It is also preferred that one of X and Y should be a tert-butyl group,that is to say, it should have the structure defined above where R is amethyl group.

It is further preferred that Z should be hydrogen or a methyl group.

The invention further provides fungicidal compositions comprising saltsof the above compounds of general formula (I) with inorganic or organicacids. Examples of salts are those with hydrochloric, nitric, sulphuric,acetic, 4-toluene-sulphonic or oxalic acid.

U.S. Pat. No. 4130646 generically describes the pharmaceutical use assedatives and tranquillisers of certain classes of compound includingthose having the general formula ##STR5## where, inter alia, R₁ may behydrogen or alkyl, m is 1 or 2 and n may be 0 or 1. There is, however,no reference to these compounds possessing fungicidal activity and themajority of them differ from the compounds defined by formula (I) abovein not showing the specified values for X and Y.

Examples of compounds conforming to formula (I) which may beincorporated in the compositions of the invention are shown in Table I.

                                      TABLE I                                     __________________________________________________________________________     ##STR6##                                                    (I)              Compound                               Melting       .sup.1 H NMR shifts      Number X     Y     Z    n   NR.sup.1 R.sup.2                                                                         Point (°C.)                                                                   Comments                                                                             (ppm from                __________________________________________________________________________                                                         TMS)                      1     H      .sub.-t-C.sub.4 H.sub.9                                                            H    1                                                                                  ##STR7##  Oil           6.24, 1Hs* 1.23,                                                              9Hs*                      2     H      .sub.-t-C.sub.4 H.sub.9                                                            H    1                                                                                  ##STR8##  Oil                                                                                   ##STR9##                                                                            6.23, 1Hs.sup.+                                                               1.31, 9Hs*                3     H      .sub. -t-C.sub.4 H.sub.9                                                           CH.sub.3                                                                           1                                                                                  ##STR10## Oil           1.31, 9hs*                4      .sub.-t-C.sub.4 H.sub.9                                                            H     H    1                                                                                  ##STR11## Oil           6.44g, 1Hs.sup.+                                                              1.22, 9Hs*                5      .sub.-t-C.sub.4 H.sub.9                                                            H     H    0                                                                                  ##STR12## 39            6.63, 1Hs.sup.+                                                               1.34, 9Hs*                6     H      .sub.-t-C.sub.4 H.sub.9                                                            H    0                                                                                  ##STR13## 53            6.61, 1Hs.sup.+                                                               1.34, 9Hs*                7      .sub.-t-C.sub.4 H.sub.9                                                            H     H    1                                                                                  ##STR14## Oil                                                                                   ##STR15##                                                                           6.28, 1Hs.sup.+                                                               1.24, 9Hs*                8     H      .sub.-i-C.sub.3 H.sub.7                                                            H    1                                                                                  ##STR16##                                         9     H      .sub.-i-C.sub.3 H.sub.7                                                            H    1                                                                                  ##STR17##                                                                                       ##STR18##                      10      .sub.-i-C.sub.3 H.sub.7                                                            H     H    1                                                                                  ##STR19##                                        11      .sub.-i-C.sub.3 H.sub.7                                                            H     H    1                                                                                  ##STR20##                                                                                       ##STR21##                      12      .sub.-i-C.sub.3 H.sub.7                                                            H     CH.sub.3                                                                           1                                                                                  ##STR22##                                                                                       ##STR23##                      13     H      .sub.-i-C.sub.3 H.sub.7                                                            CH.sub.3                                                                           1                                                                                  ##STR24##                                                                                       ##STR25##                      14     H      .sub.-i-C.sub.3 H.sub.7                                                            H    0                                                                                  ##STR26##                                                                                       ##STR27##                      15     H      .sub.-i-C.sub.3 H.sub.7                                                            H    0                                                                                  ##STR28##                                        16      .sub.-i-C.sub.3 H.sub.7                                                            H     H    0                                                                                  ##STR29##                                                                                       ##STR30##                      17      .sub.-i-C.sub.3 H.sub.7                                                            H     H    0                                                                                  ##STR31##                                        18     H      .sub.-t-C.sub.5 H.sub.11                                                           H    1                                                                                  ##STR32##                                                                                       ##STR33##                      19     H      .sub.-t-C.sub.5 H.sub.11                                                           H    1                                                                                  ##STR34##                                        20      .sub.-t-C.sub.5 H.sub.11                                                           H     H    1                                                                                  ##STR35##                                                                                       ##STR36##                      21      .sub.-t-C.sub.5 H.sub.11                                                           H     H    1                                                                                  ##STR37##                                        22     H      .sub.-t-C.sub.5 H.sub.11                                                           H    0                                                                                  ##STR38##                                                                                       ##STR39##                      23     H      .sub.-t-C.sub.5 H.sub.11                                                           H    0                                                                                  ##STR40##                                        24      .sub.-t-C.sub.5 H.sub.11                                                           H     H    0                                                                                  ##STR41##                                                                                       ##STR42##                      25      .sub.-t-C.sub.5 H.sub.11                                                           H     H    0                                                                                  ##STR43##                                        26      .sub.-t-C.sub.4 H.sub.9                                                            H     CH.sub.3                                                                           1                                                                                  ##STR44##                                                                                       ##STR45##                      27      .sub.-t-C.sub.4 H.sub.9                                                            H     CH.sub.3                                                                           1                                                                                  ##STR46##                                        28      .sub.-t-C.sub.4 H.sub.9                                                            H     CH.sub.3                                                                           0                                                                                  ##STR47##                                                                                       ##STR48##                      29       .sub.-t-C.sub.4 H.sub.9                                                           H     CH.sub.3                                                                           0                                                                                  ##STR49##                                        30     H      .sub.-t-C.sub.4 H.sub.9                                                            CH.sub.3                                                                           0                                                                                  ##STR50##                                                                                       ##STR51##                      31     H      .sub.-t-C.sub.4 H.sub.9                                                            CH.sub.3                                                                           0                                                                                  ##STR52##                                        32      .sub.-t-C.sub.4 H.sub.9                                                            H     H    1                                                                                  ##STR53##                                        33      .sub.-t-C.sub.4 H.sub.9                                                            H     H    0                                                                                  ##STR54##                                        34     H      .sub.-t-C.sub.4 H.sub.9                                                            H    1                                                                                  ##STR55##                                        35     H      .sub.-t-C.sub.4 H.sub.9                                                            H    0                                                                                  ##STR56##                                        36      .sub.-t-C.sub.4 H.sub.9                                                            H      -n-C.sub.4 H.sub.9                                                                1                                                                                  ##STR57##                                                                                       ##STR58##                      37      .sub.-t-C.sub.4 H.sub.9                                                            H      -n-C.sub.4 H.sub.9                                                                1                                                                                  ##STR59##                                        38     H      .sub.-t-C.sub.4 H.sub.9                                                             -n-C.sub.4 H.sub.9                                                                1                                                                                  ##STR60##                                                                                       ##STR61##                      39     H      .sub.-t-C.sub.4 H.sub.9                                                             -n-C.sub.4 H.sub.9                                                                1                                                                                  ##STR62##                                        40      .sub.-t-C.sub.4 H.sub.9                                                            H      -n-C.sub.4 H.sub.9                                                                0                                                                                  ##STR63##                                                                                       ##STR64##                      41      .sub.-t-C.sub.4 H.sub.9                                                            H      -n-C.sub.4 H.sub.9                                                                0                                                                                  ##STR65##                                        42     H      .sub.-t-C.sub.4 H.sub.9                                                             -n-C.sub.4 H.sub.9                                                                0                                                                                  ##STR66##                                                                                       ##STR67##                      43     H      .sub.-t-C.sub.4 H.sub.9                                                             -n-C.sub.4 H.sub.9                                                                0                                                                                  ##STR68##                                        44      .sub.-t-C.sub.4 H.sub.9                                                            H     H    1                                                                                  ##STR69##                                        45     H      .sub.-t-C.sub.4 H.sub.9                                                            H    1                                                                                  ##STR70##                                        46      .sub.-t-C.sub.4 H.sub.9                                                            H     H    1                                                                                  ##STR71##                                        47     H      .sub.-t-C.sub.4 H.sub.9                                                            H    1                                                                                  ##STR72##                                        48      .sub.-t-C.sub.4 H.sub.9                                                            H     H    1                                                                                  ##STR73##                                        49     H      .sub.-t-C.sub.4 H.sub.9                                                            H    1                                                                                  ##STR74##                                        50     H      .sub.-t-C.sub.4 H.sub.9                                                            CH.sub.3                                                                           1                                                                                  ##STR75##        Cis-dimethyl- morpholine        51     H      .sub.-t-C.sub.4 H.sub.9                                                            H    0                                                                                  ##STR76##        Cis-dimethyl- morpholine        52      .sub.-t-C.sub.4 H.sub.9                                                            H     H    0                                                                                  ##STR77##        Cis-dimethyl- morpholine        __________________________________________________________________________     .sup.+ proton on the double bond                                              *.sub.-t-C.sub.4 H.sub.9 protons                                         

The present invention also provides novel compounds which possessfungicidal activity and are suitable for use as the active ingredient ofthe compositions hereinabove defined, the compounds having the generalformula (II): ##STR78## wherein X, Y, Z, R¹ and R² are as previouslydefined; these are thuse the compounds of formula (I) where n is equalto 1.

Preferred compounds of formula (II) are those where one of X and Y is atert-butyl group. It is also preferred that Z should be hydrogen or amethyl group, and it is further preferred that the group, --NR¹ R²should be a piperidine or a 2,6-dimethylmorpholine ring.

The invention particularly provides the following novel compounds:##STR79## Compounds of general formula (I) can be prepared by treatmentof alcohols of general formula (III) wherein X, Y, Z, n, R¹ and R² areas defined above, with acid (eg. dilute sulphuric acid), preferably inthe absence of a solvent and under reflux conditions. ##STR80## Alcoholsof general formula (III) where Z is a hydrogen atom can be prepared byreduction of compounds of general formula (IV) with the usual reducingagents, for example sodium borohydride or lithium aluminium hydride.##STR81## Where Z is an alkyl group, alcohols of general formula (III)may be prepared by treatment of ketones of general formula (IV) with theappropriate alkyl magnesium halide Grignard reagent or alkyl lithium ina suitable solvent (for example diethylether or tetrahydrofuran).

Ketones of general formula (IV) can be prepared by treating a compoundof general formula (V) with formaldehyde and an amine of general formulaHNR¹ R² in the presence of an acidic catalyst under the normalconditions of the Mannich Reaction. ##STR82## Compounds of generalformula (V) can be prepared by oxidation of a hydrocarbon of generalformula (VI) by a suitable oxidising agent, for example chromiumtrioxide in a solvent such as glacial acetic acid, (see, for example, J.W. Burnham, W. P. Duncan, and E. J. Eisenbraun, Journal of OrganicChemistry 1974, 39, 10, 1416). ##STR83##

Alternatively they may be prepared by cyclisation of various substitutedphenylcarboxylic acids (VII) by methods set out in the literature (see,for example, N. G. Bromby, A. T. Peters, and F. M. Rowe, Journal of theChemical Society 1943, 1, 144). ##STR84##

It will be appreciated that in certain instances oxidation ofhydrocarbons of general formula (VI) in which X and Y representdifferent atoms or groups, with, for example, chromium trioxide in asolvent such as acetic acid can give rise to two isomeric ketones ofgeneral formula (V). Such isomeric ketones of general formula (V) can beconveniently separated by fractional distillation or by preparative highpressure liquid chromatography.

Compounds of general formula (VI) can be prepared by methods set out inthe literature (see, for example, F. C. Whitmore and W. H. Jones,Journal of American Chemical Society 1943, 65, 2088). For example6-tert-butyltetralin can be prepared by the Friedel-Crafts alkylation oftetralin using tert-butylchloride in a convenient solvent such as carbondisulphide using an appropriate catalyst, for example aluminiumchloride.

Salts of the compounds of general formula (I) may be made by methods setout in the literature.

The compounds and salts are active fungicides, particularly against thediseases:

Puccinia recondita,

Puccinia striiformis and other rusts on wheat, Puccinia hordei, Pucciniastriiformis and other rusts on barley, and rusts on other hosts e.g.coffee, apples, apples, vegetables and ornamental plants Erysiphegraminis (powdery mildew) on barley and wheat and other powdery mildewson various hosts such as

Sphaerotheca fuliginea on cucurbits (e.g. cucumber),

Podosphaera leucotricha on apples

Cercospora arachidicola on peanuts and other Cercospora species on forexample sugar beet, bananas and soya beans

Plasmopara viticola on vines

Venturia inaequalis (scab) on apples.

Some of the compounds have also shown a broad range of activitiesagainst fungi in vitro. They may have activity against variouspost-harvest diseases on fruit (e.g. Penicillium digatatum and italicumon oranges and Gloeosporium musarum on bananas). Further some of thecompounds may be active as seed dressings against: Fusarium spp.,Septoria spp., Tilletia spp. (i.e. bunt, a seed borne disease of wheat),Ustilago spp., Helminthosporium spp. and Pseudocercosporellaherpotrichoides on cereals, Rhizoctonia solani on cotton and Corticiumsasakii on rice.

The compounds can move acropetally in the plant tissue. Moreover, thecompounds can be volatile enough to be active in the vapour phaseagainst fungi on the plant.

They may also be useful as industrial (as opposed to agricultural)fungicides, e.g. in the prevention of fungal attack on wood, hides,leather and especially paint films.

The active compounds may be used as such for fungicidal purposes but aremore conveniently formulated into compositions for such usage. Theinvention thus provides a fungicidal composition comprising a compoundof general formula (I) as hereinbefore defined or a salt; and,optionally, a carrier or diluent.

The invention also provides a method of combating fungi, which comprisesapplying to a plant, to seed of a plant, or to the locus of the plant orseed, a composition, compound, or salt, as hereinbefore defined.

The active compounds and salts can be applied in a number of ways, forexample they can be applied directly to the foliage of a plant, or theycan be applied also to bushes and trees, to seeds or to other medium inwhich plants, bushes or trees are growing or are to be planted, or theycan be sprayed on, dusted on or applied as a cream or paste formulation,or they can be applied as a vapour; or as slow release granules.Application can be to any part of the plant, bush or tree, for exampleto the foliage, stems, branches or roots, or to soil surrounding theroots, or to the seed before it is planted; or to the soil generally, topaddy water or to hydroponic culture systems. The invention compoundsmay also be injected into plants or trees and they may also be sprayedonto vegetation using electrodynamic spraying techniques.

The term "plant" as used herein includes seedlings, bushes and trees.Furthermore, the fungicidal method of the invention includespreventative, protectant, prophylactic and eradicant treatment.

The compositions may be in the form of dusting powders or granulescomprising the active ingredient and a solid diluent or carrier, forexample fillers such as kaolin, bentonite, kieselguhr, dolomite, calciumcarbonate, talc, powdered magnesia, Fuller's earth, gypsum, Hewitt'searth, diatomaceous earth and China clay. Such granules can be preformedgranules suitable for application to the soil without further treatment.These granules can be made either by impregnating pellets of filler withthe active ingredient or by pelleting a mixture of the active ingredientand powdered filler. Compositions for dressing seed, for example, maycomprise an agent (for example a mineral oil) for assisting the adhesionof the composition to the seed; alternatively the active ingredient canbe formulated for seed dressing purposes using an organic solvent (forexample N-methylpyrrolidone or dimethylformamide).

The compositions may also be in the form of dispersible powders,granules or grains comprising a wetting agent to facilitate thedispersion in liquids of the powder or grains which may contain alsofillers and suspending agents.

The aqueous dispersions or emulsions may be prepared by dissolving theactive ingredient(s) in an organic solvent optionally containingwetting, dispersing or emulsifying agent(s) and then adding the mixtureto water which may also contain wetting, dispersing or emulsifyingagent(s). Suitable organic solvents are ethylene dichloride, isopropylalcohol, propylene glycol, diacetone alcohol, toluene, kerosene,methylnaphthalene, the xylenes, trichloroethylene, furfuryl alcohol,tetrahydrofurfuryl alcohol, and glycol ethers (eg. 2-ethoxyethanol and2-butoxyethanol).

The compositions to be used as sprays may also be in the form ofaerosols wherein the formulation is held in a container under pressurein the presence of a propellant, eg. fluorotrichloromethane ordichlorodifluoromethane.

The compounds can be mixed in the dry state with a pyrotechnic mixtureto form a composition suitable for generating in enclosed spaces a smokecontaining the compounds.

Alternatively, the active compounds may be used in a micro-encapsulatedform. They may also be formulated in biodegradable polymericformulations to obtain a slow, controlled release of the activesubstance.

By including suitable additives, for example additives for improving thedistribution, adhesive power and resistance to rain on treated surfaces,the different compositions can be better adapted for various utilities.

The compounds can be used as mixtures with fertilisers (eg. nitrogen-,potassium- or phosphorus-containing fertilisers). Compositionscomprising only granules of fertiliser incorporating, for example coatedwith, the compound are preferred. Such granules suitably contain up to25% by weight of the compound. The invention therefore also provides afertiliser composition comprising the compound of general formula (I) ora salt or metal complex thereof.

The compositions may also be in the form of liquid preparations for useas dips or sprays which are generally aqueous dispersions or emulsionscontaining the active ingredient in the presence of one or moresurfactants eg. wetting agent(s), dispersing agent(s), emulsifyingagent(s) or suspending agent(s); or which are spray formulations of thekind suitable for use in electrodynamic spraying techniques. Theforegoing agents can be cationic, anionic or non-ionic agents. Suitablecationic agents are quaternary ammonium compounds, for examplecetyltrimethylammonium bromide.

Suitable anionic agents are soaps, salts of aliphatic monoesters ofsulphuric acid (for example sodium lauryl sulphate), and salts ofsulphonated aromatic compounds (for example sodiumdodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate,butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- andtriisopropyl-naphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethyleneoxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkylphenols such as octyl- or nonyl-phenol and octylcresol. Other non-ionicagents are the partial esters derived from long chain fatty acids andhexitol anhydrides, and condensation products of the said partial esterswith ethylene oxide, and the lecithins. Suitable suspending agents arehydrophilic colloids (for example polyvinylpyrrolidone and sodiumcarboxymethylcellulose), and the vegetable gums (for example gum acaciaand gum tragacanth).

The compositions for use as aqueous dispersions or emulsions aregenerally supplied in the form of a concentrate containing a highproportion of the active ingredient(s), and the concentrate is to bediluted with water before use. These concentrates often should be ableto withstand storage for prolonged periods and after such storage becapable of dilution with water in order to form aqueous preparationswhich remain homogeneous for a sufficient time to enable them to beapplied by conventional and electrodynamic spray equipment. Theconcentrates may conveniently contain up to 95%, suitably 10-85%, forexample 25-60%, by weight of the active ingredient(s). Theseconcentrates suitably contain organic acids (eg. alkaryl or arylsulphonic acids such as xylenesulphonic acid or dodecyl benzenesulphonicacid) since the presence of such acids can increase the solubility ofthe active ingredient(s) in the polar solvents often used in theconcentrates. The concentrates suitably contain also a high proportionof surfactants so that sufficiently stable emulsions in water can beobtained. After dilution to form aqueous preparations, such preparationsmay contain varying amounts of the active ingredient(s) depending uponthe intended purpose, but an aqueous preparation containing 0.0005% or0.01% to 10% by weight of active ingredient(s) may be used.

The compositions of this invention can comprise also other compound(s)having biological activity, eg. compounds having similar orcomplementary fungicidal activity or compounds having plant growthregulating, herbicidal or insecticidal activity.

The other fungicidal compound can be, for example, one which is capableof combating ear diseases of cereals (eg. wheat) such as Septoria,Gibberella and Helminthosporium spp., seed and soil borne diseases anddowny and powdery mildews on grapes and powdery mildew and scab on appleetc. These mixtures of fungicides can have a broader spectrum ofactivity than the compound of general formula (I) alone; further theother fungicide can have a synergistic effect on the fungicidal activityof the compound of general formula (I). Examples of the other fungicidalcompound are carbendazim, benomyl, thiophanate-methyl, thiabendazole,fuberidazole, etridazole, dichlofluanid, cymoxanil, oxadixyl, ofurace,metalaxyl, furalaxyl, benalaxyl, fosetyl aluminium, fenarimol,iprodione, procymidone, vinclozolin, penconazole, myclobutanil,R0151297, S3308, pyrazophos, ethirimol, ditalimfos, tridermorph,triforine, nuarimol, triazbutyl, guazatine, propiconazole, prochloraz,flutriafol, chlortriafol i.e. the chemical1-(1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-hexan-2-ol, DPXH6573(1-((bis-4-fluorophenyl)methylsilyl)-methyl-1H-1,2,4-triazole,triadimefon, triadimenol, dichlobutrazol, fenpropimorph, fenpropidin,chlorozolinate, diniconazol, imazalil, fenfuram, carboxin, oxycarboxin,methfuroxam, dodemorph, BAS 454, blasticidin S, kasugamycin, edifenphos,kitazin P, cycloheximide, phthalide, probenazole, isoprothiolane,tricyclazole, pyroquilan, chlorbenzthiazone, neoasozin, polyoxin D,validamycin A, repronil, flutolanil, pencycuron, diclomezine, phenazinoxide, nickel dimethyldithiocarba-mate, techlofthalam, bitertanol,bupirimate, etaconazole, streptomycin, cypofuram, biloxazol,quinomethionate, dimethirimol, 1-(2-cyano-2-methoxyimino-acetyl)-3-ethylurea, fenapanil, tolclofosmethyl, pyroxyfur, polyram, maneb, mancozeb,captafol, chlorothalonil, anilazine, thiram, captan, folpet, zineb,propineb, sulphur, dinocap, binapactryl, nitrothalisopropyl, dodine,dithianon, fentin hydroxide, fentin acetate, tecnazene, quintozene,dichloran, copper containing compounds such as copper oxychloride,copper sulphate and Bordeaux mixture, and organomercury compounds.

The compounds of general formula (I) can be mixed with soil, peat orother rooting media for the protection of plants against seed-borne,soil-borne or foliar fungal diseases.

Suitable insecticides which may be incorporated in the compositions ofthe invention include pirimicarb, dimethoate, demeton-s-methyl,formothion, carbaryl, isoprocarb, XMC, BPMC, carbofuran, carbosulfan,diazinon, fenthion, fenitrothion, phenthoate, chlorpyrifos, isoxathion,propaphos, monocrotophos, buprofezin, ethroproxyfen and cycloprothrin.

Plant growth regulating compounds which may be used in the inventioncompositions are compounds which control weeds or seedhead formation, orselectively control the growth of less desirable plants (e.g. grasses).

Examples of suitable plant growth regulating compounds for use with theinvention compositions and compounds are the gibberellins (e.g. GA₃, GA₄or GA₇), the auxins (e.g. indoleacetic acid, indolebutyric acid,naphthoxyacetic acid or naphthylacetic acid), the cytokinins (e.g.kinetin, diphenylurea, benzimidazole, benzyladenine orbenzylaminopurine), phenoxyacetic acids (e.g. 2,4-D or MCPA),substituted benzoic acids (e.g. triiodobenzoic acid), morphactins (e.g.chlorfluoroecol), maleic hydrazide, glyphosate, glyphosine, long chainfatty alcohols and acids, dikegulac, paclobutrazol, flurprimidol,fluoridamid, mefluidide, substituted quaternary ammonium and phosphoniumcompounds (e.g. chloromequat chlorphonium or mepiquatchloride),ethephon, carbetamide, methyl-3,6-dichloroanisate, daminozide, asulam,abscisic acid, isopyrimil,1-(4-chlorophenyl)-4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylicacid, hydroxybenzonitriles (e.g. bromoxynil), difenzoquat,benzoylprop-ethyl 3,6-dichloropicolinic acid, fenpentezol, inabenfide,triapenthenol and tecnazene.

The following Examples illustrate the invention; the temperatures aregiven in degrees Centigrade (°C.).

EXAMPLE 1

This Example illustrates the preparation of6-tert-butyl-3-piperidinomethyl-1,2-dihydronaphthalene (Compound number4 of Table I). Piperidine hydrochloride (8.9 g, 0.073 mol),7-tert-butyl-1,2,3,4-tetrahydronaphthalen-1-one (7.0 g, 0.035 mol) andparaformaldehyde (2.2 g, 0.073 mol) were refluxed together in ethanol(150 ml) along with concentrated hydrochloric acid (1 ml) as a catalystfor 16 hours. The reaction mixture was concentrated under reducedpressure and the residue dissolved in water then extracted with diethylether. The resulting aqueous solution was neutralized with sodiumbicarbonate and extracted with diethyl ether (2×200 ml); the etherealextracts were dried over magnesium sulphate and concentrated underreduced pressure to give7-tert-butyl-2-piperidinomethyl-1,2,3,4-tetrahydronaphthalen-1-one (4.5g, 43% yield) as a buff coloured solid melting at 62°-3°. The7-tert-butyl-2-piperidinomethyl-1,2,3,4-tetrahydronaphthalen-1-one (4.5g, 0.015 mol) was dissolved in methanol (100 ml) and sodium borohydride(0.6 g, 0.016 mol) was added portionwise over 30 minutes at roomtemperature. It was stirred for 3 hours at room temperature then themethanol was evaporated under reduced pressure and the residue treatedwith water (100 ml) and extracted with ether (2×100 ml) which was washedwith brine, dried over magnesium sulphate and evaporated under reducedpressure to give a viscous oil (4.0 g) which crystallised on standing.Separation by column chromatography on silica gel (Merck 60) using agradient elution of petrol 60°-80° to ethyl acetate gave the alcohol astwo isomers:

(A) the faster running isomer as a white crystalline solid (1.95 g, mpt88°-90°), ¹ H nmr (CDCl₃): δ4.68, J=9.2 Hz (1 proton) thetrans-7-tert-butyl-2-piperidinomethyl-1,2,3,4-tetrahydronaphthalen-1-ol.

(B) the slower running isomer a white crystalline solid (350 mg, mpt88°-90°) ¹ H nmr (CDCl₃): δ4.86, J=4 Hz (1 proton) thecis-7-tert-butyl-2-piperidinomethyl-1,2,3,4-tetrahydronaphthalen-1-ol.

Thetrans-7-tert-butyl-2-piperidinomethyl-1,2,3,4-tetrahydronaphthalen-1-ol(2.6 g) was dissolved in 70 mls of 10% dilute sulphuric acid andrefluxed for 2 hours. After cooling the solution was washed with etherthen neutralized with sodium bicarbonate, this was extracted withdiethyl ether, dried over magnesium sulphate and evaporated underreduced pressure to give the title compound (2.0 g 81% yield) as a clearpale yellow oil. ¹ H nmr (CDCl₃): δ6.44 (1 proton).

EXAMPLE 2

This Example illustrates the preparation of7-tert-butyl-4-methyl-3-piperidinomethyl,1,2-dihydronaphthalene(Compound number 3 of Table I). Piperidine hydrochloride (12.6 g 0.103mol), 6-tert-butyl-1,2,3,4-tetrahydronaphthalen-1-one (80.0 g, 0.04 mol)and paraformaldehyde (2.64 g, 0.088 mol) were refluxed in ethanol (200ml) with concentrated hydrochloric acid (1 ml) as a catalyst for 48hours. The reaction mixture was concentrated under reduced pressure andthe residue dissolved in water then extracted with diethyl ether. Theresulting aqueous solution was neutralized with sodium bicarbonate andextracted with diethyl ether (2×200 ml); the ethereal extracts weredried over magnesium sulphate and concentrated under reduced pressure togive 6-tert-butyl-2-piperidinomethyl-1,2,3,4-tetrahydronaphthalen-1-one(10.0 g 83% yield) melting at 47°-9°.

6-Tert-butyl-2-piperidinomethyl-1,2,3,4-tetrahydronaphthalen-1-one (4.4g, 0.015 mol) in diethyl ether (40 ml) was added to an ethereal solutionof methylmagnesium iodide [prepared from methyl iodide (1.9 ml, 0.03mol) and magnesium (0.72 g, 0.03 mol)] at such a rate as to maintainreflux. It was refluxed for 1 hour, cooled and treated with saturatedammonium chloride solution (100 ml) and refluxed for 30 minutes. Theether was separated and the aqueous extracted with further ether, thecombined extracts were dried over magnesium sulphate and evaporated togive a solid residue. Purification by column chromatography using silicagel with ethyl acetate: petroleum 60°-80°, 3:7 gave6-tert-butyl-1-methyl-2-piperidinomethyl-1,2,3,4-tetrahydronaphthalen-1-ol(3.9 g, 82% yield) a white solid melting at 113°-4°.6-tert-butyl-1-methyl-2-piperidinomethyl-1,2,3,4-tetrahydronaphthalen-1-ol(3.7 g, 0.012 mol) was refluxed in dilute sulphuric acid (50 ml, 10%)for 45 minutes. After cooling it was neutralized with sodium hydroxide,extracted with ether, dried over magnesium sulphate and evaporated underreduced pressure to give the title compound (3.5 g, 98% yield) as aclear oil.

EXAMPLE 3

This Example illustrates the preparation of7-tert-butyl-3-cis-(2,6-dimethylmorpholinomethyl)-1,2-dihydronaphthalene(Compound No. 2 in Table I). 2,6-Dimethylmorpholine hydrochloride (12.1g, 0.08 mol), 6-tert-butyl-1,2,3,4-tetrahydronaphthalen-1-one (8.1 g,0.04 mol) and paraformaldehyde (2.4 g, 0.08 mol) were refluxed togetherin ethanol (150 ml) with concentrated hydrochloric acid (1 ml) as acatalyst for 16 hours. The reaction mixture was concentrated underreduced pressure and the residue dissolved in water then extracted withdiethyl ether. The resulting aqueous solution was neutralised withsodium bicarbonate and extracted with diethyl ether (2×200 ml); theethereal extracts were dried over anhydrous magnesium sulphate andconcentrated under reduced pressure to give an orange oil. This oil waspurified by hplc (silica eluted with ethyl acetate/petroleum ether 1:1)to give6-tert-butyl-2-cis-(2,6-dimethylmorpholinomethyl)-1,2,3,4-tetrahydronaphthalen-1-one(5.1 g, 39%).

6-Tert-butyl-2-cis-(2,6-dimethylmorpholinomethyl)-1,2,3,4-tetrahydronaphthalen-1-one(4.6 g, 0.014 mol) was dissolved in methanol (100 ml) and sodiumborohydride (0.5 g, 0.013 mol) was added portionwise over 30 minutes atroom temperature. It was stirred for 3 hours at room temperature thenthe methanol was evaporated under reduced pressure and the residuetreated with water (100 ml) and extracted with ether (2×100 ml) whichwas washed with brine, dried over magnesium sulphate and evaporatedunder reduced pressure to give an oil. This was purified by columnchromatography (silica eluted with ethyl acetate/petroleum ether 2:3) togivetrans-6-tert-butyl-cis-(2,6-dimethylmorpholinomethyl)-1,2,3,4-tetrahydronaphthalen-1-ol(2.0 g, 43%) as a clear oil.

Thetrans-6-tert-butyl-cis-(2,6-dimethylmorpholinomethyl)-1,2,3,4-tetrahydronaphthalen-1-ol(0.7 g, 00021 mol) was dissolved in 10% sulphuric acid (30 ml) andrefluxed for 2 hours. After cooling the solution was washed with etherthen neutralised with sodium bicarbonate; this was extracted withdiethyl ether dried over anhydrous magnesium sulphate and evaporatedunder reduced pressure to give the title compound (0.6 g, 90%) as aclear oil. ¹ H NMR (CDCl₃): δ6.23 (1 proton).

EXAMPLE 4

An emulsifiable concentrate is made up by mixing the ingredients, andstirring the mixture until all the constituents are dissolved.

    ______________________________________                                        Compound No 5 of Table I                                                                             10%                                                    Isophorone             25%                                                    Calcium dodecylbenzenesulphonate                                                                      5%                                                    Nonylphenolethoxylate (13 moles                                                                      10%                                                    ethylene oxide)                                                               Alkyl benzenes         50%                                                    ______________________________________                                    

EXAMPLE 5

The active ingredient is dissolved in methylene dichloride and theresultant liquid sprayed onto the granules of attapulgite clay. Thesolvent is then allowed to evaporate to produce a granular composition.

    ______________________________________                                        Compound No 6 of Table I                                                                            5%                                                      Attapulgite granules 95%                                                      ______________________________________                                    

EXAMPLE 6

A composition suitable for use as a seed dressing is prepared bygrinding and mixing the three ingredients.

    ______________________________________                                        Compound No 5 of Table I                                                                           50%                                                      Mineral oil           2%                                                      China clay           48%                                                      ______________________________________                                    

EXAMPLE 7

A dustable powder is prepared by grinding and mixing the activeingredient with talc.

    ______________________________________                                        Compound No 6 of Table I                                                                            5%                                                      Talc                 95%                                                      ______________________________________                                    

EXAMPLE 8

A suspension concentrate is prepared for chemicals which are largelyinsoluble solids by ball milling, for example, the constituents set outbelow, to form an aqueous suspension of the ground mixture with water.

    ______________________________________                                        Compound No 5 of Table I                                                                           40%                                                      Sodium lignosulphonate                                                                             10%                                                      Bentonite clay        1%                                                      Water                49%                                                      ______________________________________                                    

This formulation can be used as a spray by diluting into water orapplied directly to seed.

EXAMPLE 9

A wettable powder formulation is made by mixing together the ingredientsset out below and then grinding the mixture until all are thoroughlymixed.

    ______________________________________                                        Compound No 6 of Table I                                                                           25%                                                      Sodium lauryl sulphate                                                                              2%                                                      Sodium lignosulphonate                                                                              5%                                                      Silica               25%                                                      China clay           43%                                                      ______________________________________                                    

EXAMPLE 10

A Col formulation was prepared by ball-milling the constituents set outbelow and then forming an aqueous suspension of the ground mixture withwater.

    ______________________________________                                        Compound No 5 of Table I                                                                           40%                                                      "Dispersol" T        10%                                                      "Lubrol" APN5         1%                                                      Water                                                                         ______________________________________                                    

EXAMPLE 11

A dispersible powder formulation was made by mixing together theingredients set out below and then grinding the mixture until all werethoroughly mixed.

    ______________________________________                                        Compound No 6 of Table I                                                                           25%                                                      "Aerosol" OT/B        2%                                                      "Dispersol" A.C.      5%                                                      China clay           28%                                                      Silica               40%                                                      ______________________________________                                    

In Examples 4 to 11 the proportions of the ingredients given are byweight. The remaining compounds of Table I were all similarly formulatedas per Examples 4 to 11.

There now follows an explanation of the compositions or substancesrepresented by the various Trade Marks mentioned above.

DISPERSOL T and AC: a mixture of sodium sulphate and a condensate offormaldehyde with sodium naphthalene sulphonate

LUBROL APN5: a condensate of nonyl phenol (1 mole) with naphthaleneoxide (5.5 moles)

AEROSOL OT/B: dioctyl sodium sulphosuccinate

EXAMPLE 12

The compounds were tested against a variety of mainly foliar fungaldiseases of plants. The techniques employed were as follows.

For all tests the plants were grown in John Innes Potting Compost (No. 1or 2) in 4 cm diameter minipots. The test compounds were formulatedeither by bead milling with aqueous Dispersol T or as a solution inacetone or acetone/ethanol which was diluted to the requiredconcentration immediately before use. The solutions or suspensions (100ppm ai.) were sprayed on the foliage and applied to the roots of theplant via the soil. The sprays were applied to maximum retention and theroot drenches to a final concentration equivalent to approximately 40ppm ai./dry soil. Tween 20, to give a final concentration of 0.05%, wasadded when the sprays were applied to cereals. (a.i. means "activeingredient").

Most were protectant tests where the compound was applied to the soiland roots and to the foliage one or two days before the plant wasinoculated with the pathogen. (Erysiphe graminis was a one day eradicanttest). The foliar pathogens were applied by spraying as sporesuspensions onto the leaves of the test plants.

After inoculation, the plants were placed in an appropriate environmentto allow infection to proceed and then incubated until the disease wasready for assessment. The period between inoculation and assessmentvaried from four to fourteen days according to the disease and theenvironment.

Disease control was recorded using the following grading system:

4=no disease

3=trace to 5% of disease on untreated plants

2=6-25% of disease on untreated plants

1=26-59% of disease on untreated plants

0=60-100% of disease on untreated plants

The results are shown in Table II.

                                      TABLE II                                    __________________________________________________________________________            PUCCINIA                                                                             VENTURIA                                                                              CERCOSPORA                                                                              PLASMOPARA                                                                            ERYSIPHE                             COMPOUND                                                                              RECONDITA                                                                            INAEQUALIS                                                                            ARACHIDICOLA                                                                            VITICOLA                                                                              GRAMINIS HORDEI                      NUMBER  (WHEAT)                                                                              (APPLES)                                                                              (PEANUTS) (VINES) (BARLEY)                             __________________________________________________________________________    1       2      0       0         0       4                                    2       0      3       4         0       4                                    3       3      0       4         0       4                                    4       0      0       2         0       4                                    5       3      2       0         1       4                                    6       2      0       0         4       0                                    7       2      4       4         0       4                                    __________________________________________________________________________

We claim:
 1. A fungicidal composition comprising a diluent or carrierand as an active ingredient (a) a compound having the general formula##STR85## or a stereoisomer thereof, wherein one of X and Y representshydrogen and the other represents the group ##STR86## in which R ishydrogen, methyl or ethyl; Z represents an alkyl group containing fromone to four carbon atoms; R¹ and R² together with the adjacent nitrogenatom represent a piperidine ring optionally substituted by one or morealkyl, aryl, hydroxy, alkoxy, aryloxy or aralkyl groups; and n is 1; or(b) an acid addition salt of such a compound.
 2. A composition asclaimed in claim 1, wherein in the active compound one of X and Y is atert-butyl group.
 3. A composition as claimed in claim 1, wherein theactive compound has the formula: ##STR87##
 4. A method of combatingfungi which comprises applying to a plant, to seed of a plant or to thelocus of a plant or seed, a fungicidal composition as claimed in any oneof claims 1 2, or 3.